Block copolymerization of allene derivatives with isocyanides by the coordination polymerization with ?-allylnickel catalyst

Abstract

A living block copolymerization of allene derivatives with 1‐phenylethyl isocyanide (3) using [(allyl)NiOCOCF3]2 (1) is described. After complete polymerization of allene monomers such as n‐octyloxyallene (2A) with 1, further addition of 3 to the reaction system yielded the corresponding block copolymers in high yield. For instance, a block copolymer (4A, Mn = 39,600, Mw/Mn = 1.20) was obtained in 96% yield by the addition of 3 ([3]/[1] = 250) to the living solution of poly(n‐octyloxyallene) (Mn = 14,400, Mw/Mn = 1.03) prepared by the polymerization of 2A in the ratio of [2A]/[1] = 90. The resulting copolymer was a brownish orange gum or a solid, depending on the length of each of the segments. The solubility of the block copolymers could be controlled by the allene components. The copolymer of 2A with 3 having appropriate length of segments was soluble in n‐hexane, while that of methoxyethoxyethoxyallene (2D) with 3 was soluble in methanol. © 1997 John Wiley & Sons, Inc.

Synthesis of PS-b-PPOA-b-PS triblock copolymer via sequential free radical polymerization and ATRP

“…FT‐IR spectra were recorded on a Nicolet AVATAR‐360 FTIR spectrophotometer with a resolution of 4 cm −1 . All 1 H (500 MHz) and C (125 MHz) NMR analyses were performed on a Bruker Avance 500 spectrometer in CDCl 3 , TMS ( 1 H NMR) and CDCl 3 ( 13 C NMR) were used as internal standards. Elemental analysis was carried out on a Carlo‐Erba1106 system.…”

“…1 H NMR (500 MHz, CDCl 3 , δ): 1.75 (6H, C H 3 C(CN)CH 2 CH 2 CO 2 ), 1.95 (6H, C H 3 CHBr), 2.61 (8H, CH 3 C(CN)C H 2 C H 2 CO 2 ), 4.59 (2H, CH 3 C H Br), 7.13 (8H, C 6 H 4 ). C NMR (125 MHz, CDCl 3 , δ): 21.4, 24.0, 29.1, 33.0, 39.4, 117.4, 122.2, 148.0, 168.5, 169.7. A nal .…”

“…Element analysis: Br% = 1.70%. FT‐IR (KBr): ν = 3070, 3039, 2952, 2926, 1761 (CO), 1675, 1643 (CC), 1595, 1491, 1456, 1337, 1290, 1227, 1171, 1135, 1030, 892, 752, 691 (cm −1 ); 1 H NMR (500 MHz, CDCl 3 , δ): 1.61 (6H, C H 3 CCN), 1.93 (6H, C H 3 CHBr), 2.55 (2H × x, =C‐C H 2 ), 4.57 (2H, CH 3 C H Br), 5.00 (1H × y, CH 2 = CC H O), 5.21 (2H × y, C H 2 = CCHO), 6.85, 6.92, 7.01, 7.16 (1H × x, CC H OC 6 H 5 and 5H, C 6 H 5 ); C NMR (125 MHz, CDCl 3 , δ): 19.4, 21.3, 25.5, 28.9, 30.4, 33.5, 35.9, 39.4, 72.6, 112.5, 115.7, 116.6, 120.8, 122.7, 141.8, 158.3, 169.0.…”

“…Block copolymerization of allene derivatives also can be conducted because of the stability of living π‐allylnickel end groups and the molecular weights of the corresponding block copolymers could be tuned by the feeding ratio . Moreover, block copolymers of allene derivatives with butadiene, isocyanides, or 3‐hexylthiophene have been synthesized by sequential feeding because all these monomers can also be polymerized with [( η 3 ‐allyl)NiOCOCF 3 ] 2 .…”

Block copolymerization of allene derivatives with 1,3-butadiene by living coordination polymerization with ?-allylnickel catalyst

“…2 Because of the stability of the living -allylnickel ends of the polymers, block copolymerization of two kinds of substituted allenes or of allene derivatives with isocyanides can be attained by the two-stage coordination polymerization process in which the molecular weight and the length of each segment of the block copolymers are successfully controlled by the monomer feed ratio (Scheme 1). 3,4 Several researchers reported the living coordination polymerization of 1,3-butadiene (2) by 1 in which the propagating end also has an -allylnickel structure. 5,6 Accordingly, the coordination polymerization of allene derivatives is expected to take place from the living polybutadiene to produce block copolymers of 1,3-butadiene with allene derivatives.…”